Patents Represented by Attorney George F. Helfrich
  • Patent number: 5428102
    Abstract: A series of polyimides based on the dianhydride of 1,4-bis(3,4-dicarboxyphenoxy)benzene (HQDEA) or on 2,2-bis[4(3-aminophenoxy)phenyl]hexafluoropropane (3-BDAF) are evolved from high molecular weight polyamic acid solutions yielding flexible free-standing films and coatings in the fully imidized form which have a dielectric constant in the range of 2.5 to 3.1 at 10 GHz.
    Type: Grant
    Filed: May 2, 1994
    Date of Patent: June 27, 1995
    Assignee: The United States of America as represented by the United States National Aeronautics and Space Administration
    Inventors: Anne K. St. Clair, Terry L. St. Clair, William P. Winfree
  • Patent number: 5426234
    Abstract: A composition of matter having the general structure: ##STR1## (wherein X is F, Cl, or NO.sub.2, and Y is CO, SO.sub.2 or C(CF.sub.3).sub.2) is employed to terminate a nucleophilic reagent, resulting in the exclusive production of phenylethynyl terminated reactive oligomers which display unique thermal characteristics. A reactive diluent having the general structure: ##STR2## (wherein R is any aliphatic or aromatic moiety) is employed to decrease the melt viscosity of a phenylethynyl terminated reactive oligomer and to subsequently react therewith to provide a thermosetting material of enhanced density. These materials have features which make them attractive candidates for use as composite matrices and adhesives.
    Type: Grant
    Filed: May 16, 1994
    Date of Patent: June 20, 1995
    Assignee: The United States of America as represented by the Administrator of the National Aeronautics and Space Administration
    Inventors: Robert G. Bryant, Brian J. Jensen, Paul M. Hergenrother
  • Patent number: 5418300
    Abstract: Crystalline imide/arylene ether block copolymers are prepared by reacting anhydride terminated poly(amic acids) with amine terminated poly(arylene ethers) in polar aprotic solvents and chemically or thermally cyclodehydrating the resulting intermediate poly(amic acids). The block copolymers of the invention have one glass transition temperature or two, depending on the particular structure and/or the compatibility of the block units. Most of these crystalline block copolymers form tough, solvent resistant films with high tensile properties. While all of the copolymers produced by the present invention are crystalline, testing reveals that copolymers with longer imide blocks or higher imide content have increased crystallinity.
    Type: Grant
    Filed: April 8, 1994
    Date of Patent: May 23, 1995
    Assignee: The United States of America as represented by the Administrator, National Aeronautics and Space Administration
    Inventors: Brian J. Jensen, Paul M. Hergenrother, Robert G. Bass
  • Patent number: 5412059
    Abstract: Novel molecular weight controlled and endcapped polybenzimidazoles (PBI) are prepared by the aromatic nucleophilic displacement reaction of di(hydroxyphenylbenzimidazole) monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The PBI are endcapped with mono(hydroxyphenyl)benzimidazoles. The polymerizations are carried out in polar aprotic solvents such as N-methyl-2-pyrrolidinone or N,N-dimethylacetamide using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. Mono(hydroxyphenyl)benzimidazoles are synthesized by reacting phenyl-4-hydroxybenzoate with aromatic (o-diamine)s in diphenylsulfone. Molecular weight controlled and endcapped PBI of new chemical structures are prepared that exhibit a favorable combination of physical and mechanical properties.
    Type: Grant
    Filed: April 5, 1993
    Date of Patent: May 2, 1995
    Assignee: The United States of America as represented by the Administrator of the National Aeronautics and Space Administration
    Inventors: John W. Connell, Paul M. Hergenrother, Joseph G. Smith, Jr.
  • Patent number: 5412066
    Abstract: Four phenylethynyl amine compounds--3 and 4-aminophenoxy-4'-phenylethynylbenzophenone, and 3 and 4-amino-4'-phenylethynylbenzophenone--were readily prepared and were used to endcap imide oligomers. Phenylethynyl-terminated amide acid oligomers and phenylethynyl-terminated imide oligomers with various molecular weights and compositions were prepared and characterized. These oligomers were cured at 300.degree. C. to 400.degree. C. to provide crosslinked polyimides with excellent solvent resistance, high strength and modulus and good high temperature properties. Adhesive panels, composites, films and moldings from these phenylethynyl terminated imide oligomers gave excellent mechanical performance.
    Type: Grant
    Filed: March 3, 1994
    Date of Patent: May 2, 1995
    Assignee: Ther United States of America as represented by the Administrator of the National Aeronautics and Space Administration
    Inventors: Paul M. Hergenrother, Robert G. Bryant, Brian J. Jensen, Stephen J. Havens
  • Patent number: 5410012
    Abstract: Novel poly(N-arylenebenzimidazole)s (PNABIs) are prepared by the aromatic nucleophilic displacement reaction of novel di(hydroxyphenyl-N-arylene benzimidazole) monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The polymerizations are carried out in polar aprotic solvents such as N-methyl-2-pyrrolidinone or N,N-dimethylacetamide using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. The di(hydroxyphenyl-N-arylenebenzimidazole) monomers are synthesized by reacting phenyl-4-hydroxybenzoate with bis(2-aminoanilino)arylenes in diphenylsulfone. Moderate molecular weight PNABIs of new chemical structures were prepared that exhibit a favorable combination of physical and mechanical properties. The use of the novel di(hydroxyphenyl-N-arylenebenzimidazole)s permits a more economical and easier way to prepare PNABIs than previous routes.
    Type: Grant
    Filed: March 5, 1993
    Date of Patent: April 25, 1995
    Assignee: The United States of America as represented by the Administrator of the National Aeronautics and Space Administration
    Inventors: John W. Connell, Paul M. Hergenrother, Joseph G. Smith, Jr.
  • Patent number: 5405683
    Abstract: A shaped towpreg ribbon having a cross-sectional geometry which promotes intimate lateral contact between adjacent composite tows was prepared. The cross-sectional geometry is non-rectangular and promotes intimate lateral contact between adjacent towpreg ribbons during normal processing.
    Type: Grant
    Filed: October 20, 1993
    Date of Patent: April 11, 1995
    Assignee: The United States of America as represented by the Administrator of the National Aeronautics and Space Administration
    Inventors: Donald A. Sandusky, Joseph M. Marchello, Robert M. Baucom
  • Patent number: 5395477
    Abstract: An apparatus and method were developed for providing a uniform, consolidated, unidirectional, continuous, fiber-reinforced polymeric material. The apparatus comprises a supply means, a forming means, a shaping means, and a take-up means. The forming means further comprises a pre-melting chamber and a stationary bar assembly. The shaping means is a loaded cooled nip-roller apparatus. Forming takes place by heating a polymeric prepreg material to a temperature where the polymer becomes viscous and applying pressure gradients at separate locations along the prepreg material. Upon exiting the forming means, the polymeric prepreg material is malleable, consolidated and flattened. Shaping takes place by passing the malleable, consolidated, flattened prepreg material through a shaped, matched groove in a loaded, cooled nip-roller apparatus to provide the final solid product.
    Type: Grant
    Filed: October 20, 1993
    Date of Patent: March 7, 1995
    Assignee: The United States of America as represented by the Administrator of the National Aeronautics and Space Administration
    Inventor: Sandusky Donald A.
  • Patent number: 5378795
    Abstract: Soluble, amorphous, aromatic polyazomethine polymers and copolymers were prepared by reacting a dialdehyde monomer with a diamine monomer containing trifluoromethylbenzene and various combinations thereof in a solvent, such as N,N-dimethylacetamide. The reaction was heated to reflux yielding a polyazomethine which, after cooling to room temperature, was precipitated. These polymers and copolymers may be used to make films, coatings, composites and adhesives.
    Type: Grant
    Filed: July 30, 1993
    Date of Patent: January 3, 1995
    Assignee: The United States of America as represented by the Administrator of the National Aeronautics and Space Administration
    Inventor: Robert G. Bryant
  • Patent number: 5376209
    Abstract: An assembly of an article and a polyimide composition is prepared. The assembly resists dimensional change, delamination, or debonding when exposed to changes in temperature. An article is provided. A polyamic acid solution which yields a polyimide having a low coefficient of thermal expansion (CTE) was prepared. Equimolar quantities of an aromatic diamine and an aromatic dianhydride were reacted in a solvent medium to form a polyamic acid solution. A metal ion-containing additive was added to the solution. Examples of this additive are: TbCl.sub.3, DyCl.sub.3, ErCl.sub.3, TmCl.sub.3, Al(C.sub.5 H.sub.7 O.sub.2).sub.3, and Er.sub.2 S.sub.3. The polyamic acid solution was imidized and is combined with the article to form the assembly.
    Type: Grant
    Filed: October 20, 1993
    Date of Patent: December 27, 1994
    Assignee: The United States of America as represented by the Administrator of the National Aeronautics and Space Administration
    Inventors: Diane M. Stoakley, Anne K. St. Clair
  • Patent number: 5374400
    Abstract: A quick-response, real-time gaseous measurement system allows for the continuous sampling of a low pressure gaseous environment. A sample of test gas from the low pressure gaseous environment is continuously extracted and pumped to a structural tee joint which is open to the atmosphere at one end to maintain the test gas at a constant pressure. The structural tee joint communicates at the other end with a heater for maintaining the test gas at a constant temperature. From the heater, the test gas is sent to a sensor which develops a voltage that is proportional to the partial pressure of the gaseous component to be measured in the test gas, a constant flow rate to test gas being provided through the heater and sensor. Since test gas pressure, temperature, and flow rate are being held constant, changes in sensor voltage are attributable only to changes in the concentration of the measured gas component.
    Type: Grant
    Filed: May 7, 1992
    Date of Patent: December 20, 1994
    Assignee: The United States of America as represented by the Administrator of the National Aeronautics and Space Administration
    Inventors: Danny R. Sprinkle, Tony T. D. Chen, Sushil K. Chaturvedi
  • Patent number: 5367161
    Abstract: A high purity, hyperthermal, continuous beam atomic oxygen source capable of retrofitting to existing UHV systems has been developed. The instrument complements a general system capability, while its small size and simplicity of design permits tailoring the instrument for most experimental geometries. The flux level presently available is near 1.times.10.sup.14 cm.sup.-2 s.sup.-1 (.sup.3 P) but may be extended toward the theoretical limit of 3.times.10.sup.15 cm.sup.-2 s.sup.-1. The energy distribution of the emitted neutrals shows that the mean kinetic energy is about the same as observed for the ions or about 5 eV. The energy of the oxygen atoms may be substantially reduced for other applications by collision with a temperature controlled, non-reactive surface (with a concomitant spread in the energy distribution).
    Type: Grant
    Filed: July 2, 1993
    Date of Patent: November 22, 1994
    Assignee: The United States of America as represented by the Administrator of the National Aeronautics and Space Administration
    Inventors: Ronald A. Outlaw, Mark R. Davison
  • Patent number: 5367046
    Abstract: A high temperature resistant fiber, especially a polyimide fiber, having a dielectric constant less than 3 is prepared by first reacting 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane with 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride in an aprotic solvent to form a polyamic acid resin solution. The polyamic acid resin solution is then extruded into a coagulation medium to form polyamic acid fibers, which are thermally cured to their polyimide form. Alternatively, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane with 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride to form a polyamic acid, and the polyamic acid is chemically converted to its polyimide form. The polyimide is then dissolved in a solvent to form a polyimide resin solution, and the polyimide resin is extruded into a coagulation medium to form a polyimide wet gel filament. In order to obtain polyimide fibers of increased tensile properties, the polyimide wet gel filaments are stretched at elevated temperatures.
    Type: Grant
    Filed: April 10, 1992
    Date of Patent: November 22, 1994
    Assignee: The United States of America as represented by the Administrator of the National Aeronautics and Space Administration
    Inventors: William E. Dorogy, Jr., Anne K. St. Clair
  • Patent number: 5344982
    Abstract: Diamines containing pendent ethynyl and substituted ethynyl groups are synthesized. These diamines are reacted with dianhydrides to form polyamide acids, which are chemically or thermally cyclodehydrated to form polyimides and copolyimides with pendent ethynyl groups. Upon heating, the pendent ethynyl groups react to form crosslinked resins that are useful as adhesives, composite matrices, coatings, moldings and films.
    Type: Grant
    Filed: April 2, 1993
    Date of Patent: September 6, 1994
    Assignee: The United States of America as represented by the Administrator of the National Aeronautics and Space Administration
    Inventors: Paul M. Hergenrother, Brian J. Jensen
  • Patent number: 5343035
    Abstract: A strain sensor uses an optical fiber including a strain sensitive portion and at least one strain insensitive portion. The strain sensitive portion is mounted on the surface of a structure at a location where a strain is desired to be measured. The strain insensitive portion(s) may be fused to the strain sensitive portion to transmit light therethrough, so that the resulting pattern may be detected to determine the amount of strain by comparison with a similar fiber not subjected to strain, or with the light pattern produced when the fiber is not under strain.
    Type: Grant
    Filed: December 21, 1992
    Date of Patent: August 30, 1994
    Assignee: The United States of America as represented by the Administrator of the National Aeronautics and Space Administration
    Inventors: Claudio O. Egalon, Robert S. Rogowski
  • Patent number: 5343550
    Abstract: An optical fiber comprising a fiber core having a longitudinal symmetry axis is provided. An active cladding surrounds a portion of the fiber core and comprises light-producing sources which emit light in response to chemical or light excitation. The cladding sources are oriented traversely with respect to the longitudinal axis of the fiber core. This polarization results in a superior power efficiency compared to active cladding sources that are randomly polarized or longitudinally polarized parallel with the longitudinal symmetry axis.
    Type: Grant
    Filed: February 25, 1993
    Date of Patent: August 30, 1994
    Assignee: The United States of America as represented by the United States National Aeronautics and Space Administration
    Inventors: Claudio O. Egalon, Robert S. Rogowski
  • Patent number: 5338826
    Abstract: A structure which is effective as an electrical insulator or as a transmitter-receiver of electromagnetic energy is prepared by providing a suitable substrate and covering the substrate with an adhering layer of a low dielectric, high temperature, linear aromatic polyimide.
    Type: Grant
    Filed: September 28, 1992
    Date of Patent: August 16, 1994
    Assignee: The United States of America as represented by the Administrator of the National Aeronautics and Space Administation
    Inventors: Anne K. St. Clair, Terry L. St. Clair, William P. Winfree
  • Patent number: 5338806
    Abstract: A high temperature semi-interpenetrating polymer network (semi-IPN) was developed which had significantly improved processability, damage tolerance and mechanical performance, when compared to the commercial Thermid.RTM. materials. This simultaneous semi-IPN was prepared by mixing a thermosetting polyimide with a thermoplastic monomer precursor solution (NR-150B2) and allowing them to react upon heating. This reaction occurs at a rate which decreases the flow and broadens the processing window. Upon heating at a higher temperature, there is an increase in flow. Because of the improved flow properties, broadened processing window and enhanced toughness, high strength polymer matrix composites, adhesives and molded articles can now be prepared from the acetylene endcapped polyimides which were previously inherently brittle and difficult to process.
    Type: Grant
    Filed: January 31, 1992
    Date of Patent: August 16, 1994
    Assignee: The United States of America as represented by the Administrator of the National Aeronautics and Space Administration
    Inventor: Ruth H. Pater
  • Patent number: 5331063
    Abstract: This invention is a semi-interpenetrating polymer network which includes a high performance thermosetting polyimide having a nadic end group acting as a crosslinking site and a high performance linear thermoplastic polyimide having the following repeating unit. ##STR1## wherein Z=C or SO.sub.2. Provided is an improved high temperature matrix resin which is capable of performing in the 200.degree. to 300.degree. C. range. This resin has significantly improved toughness and microcracking resistance, excellent processability, mechanical performance and moisture and solvent resistances.
    Type: Grant
    Filed: October 27, 1992
    Date of Patent: July 19, 1994
    Assignee: The United States of America as represented by the Administrator of the National Aeronautics and Space Administration
    Inventors: Ruth H. Pater, Norman J. Johnston
  • Patent number: 5317078
    Abstract: Di(hydroxyphenyl)benzimidazole monomers were prepared from phenyl-4-hydroxybenzoate and aromatic bis(o-diamine)s. These monomers were used in the synthesis of soluble polybenzimidazoles. The reaction involved the aromatic nucleophilic displacement of various di(hydroxyphenyl)benzimidazole monomers with activated aromatic dihalides or activated aromatic dinitro compounds in the presence of an alkali metal base. These polymers exhibited lower glass transition temperatures, improved solubility, and better compression moldability over their commercial counterparts.
    Type: Grant
    Filed: October 30, 1991
    Date of Patent: May 31, 1994
    Assignee: The United States of America as represented by the Administrator of the National Aeronautics and Space Administration
    Inventors: John W. Connell, Paul M. Hergenrother, Joseph G. Smith